Antimicrobial textile materials

ABSTRACT

TEXTILE MATERIALS CONTAINING REACTIVE HYDROGEN SITES, E.G. CELLULOSE SUCH AS COTTON, ARE TREATED WITH COMPOUNDS WICH, THROUGH REACTION WITH THE REACTIVE HYDROGEN SITES, INTRODUCE ANION-ACTIVE SITES. THESE ANION-ACTIVE SITES ARE THEREAFTER CHEMICALLY COMBINED IN SALT FORM WITH CATIONACTIVE MICROBICIDES. FOR EXAMPLE, A COTTON FABRIC IS REACTED WITH THE CHLORINE ATOMS OF P-N(4,6-DICHLORO)-STRIAZINYLAMINOBENZENE-CARBOXYLIC OR SULFONIC ACID AND THE ACID GROUP IS THEREAFTER REACTED WITH A BACTERICIDAL QUATERNARY AMMONIUM SALT OR AN N-CHLORO-PHENYL-ALKYLENE POLYAMINE. THE RESULTING PRODUCTS ARE BACTERICIDAL, FREE FROM ATTACK BY MILDEW AND SUITABLE FOR AUTOSTERILE SURGICAL DRESSINGS.

United States Patent 3,817,702 ANTIMICROBIAL TEXTILE MATERIALS 'WilfriedPaulus, Krefeld-Bockum, and Otto Pauli, Krefeld, Germany, assignors toBayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Dec. 2,1970, Ser. No. 94,532 Claims priority, application Germany, Dec. 16,1969,

Int. Cl. D06m 13/00 vs. C]. 8- 120 16 Claims ABSTRACT OF THE DISCLOSURETextile materials containing reactive hydrogen sites, e.g. cellulosicssuch as cotton, are treated with compounds which, through reaction withthe reactive hydrogen sites, introduce anion-active sites. Theseanion-active sites are thereafter chemically combined in salt form Withcationactive microbicides. For example, a cotton fabric is reacted withthe chlorine atoms ofp-N(4,6-dich1oro)-striazinylaminobenzene-carboxylic or -sulfonic acidand the acid group is thereafter reacted with a bactericidal quaternaryammonium salt or an N-chloro-phenyl-alkylene polyamine.

, The resulting products are bactericidal, free from attack by mildewand suitable for autosterile surgical dressings.

The present invention relates to the antimicrobial finishing of textilematerials, especially cellulose-containing textile material.

Textile articles are often prone to attack by microorganisms such asmildew, fungi, and the like, resulting in discoloration, odor and,frequently, destruction. Attempts have been made to overcome thisproblem by impregnation with various agents but this is often attendedby a change in hand, e.g. stiffening, by its own change in color, lossof abrasion resistance, etc. Moreover, the treatment is not permanent,the agent being lost in washing or dry cleaning. It is accordingly anobject of the present invention to provide textile materials which areresistant to microorganisms but retain all the usual desirablecharacteristics of textiles and which, further, permanently retain thedesired properties.

These. and other objects and advantages are realized in accordance withthe present invention which provides a process wherein the textilematerial is linked chemically with a reactive ionic substance, wherebyit is made partially anion-active, and the resulting partiallyanion-active textile material is finished by treatment with acationactive microbicide.

Any textile material having a reactive hydrogen may be used for theinstant purposes including cotton, rayon, paper, cellulose acetate,polyvinyl alcohol, wool, and the like, the cellulosics being especiallypreferred.

As examples of reactive ionic substances which can be linked chemicallywith the textile material, for example cotton, so that a lastingly,partially anion-active textile material is formed, there may bementioned p-N(4,6-dichloro-)s-triazinyl-aminobenzoic acid andp-N-(4,6-dichloro-)s-triazinyl-aminobenzene-sulfonic acid as well asmonochloroacetic acid, chloromethylphosphonic acid and unsaturatedaliphatic carboxylic acids, for example haloacrylic acids andacetylenemonoor dicarboxylic acid. Such compounds aifix themselves tothe textile base by losing their halogen atoms which react with thereactive hydrogen of the base or by condensation at the unsatu-3,817,702 Patented June 18, 1974 without loss of anti-microbialeffectiveness, bactericidal quaternary ammonium salts andN-chloro-phenyl-alkylenepolyamines are suitable; for examplebenzyl-dimethyltetradecylammonium chloride,3,4-dichlorobenzyl-dimethyl-dodecylammonium chloride, N-pentachlorophenyl-N dimethylbenzyltrimethylenediaminium chloride, N-pentachlorophenyl-N -dimethyl-(3,4-dichloro)benzyltrimethylenediaminium chloride (cf. Deutsche Offenlegungschrift (GermanPublished Specification) 1,493,745) and N pentachlorophenylhexamethylenediamine acetate (cf. Belgian Patent Specification 725,992).

The production of partially anion-active material, for example, cottonfabric, can be effected by treating the fabric with a 2-5 strengthalkaline-aqueous solution of the reactive ionic substances concerned,possibly with addition of an electrolyte (for example NaCl, Na SO for10-40 minutes at 40-60 C. It is also possible to proceed by impregnatingthe fabric at room temperature with an alkaline-aqueous solution of thereactive ionic substances concerned, subsequently squeezing off and,possibly after a preliminary drying at about 70 C., thermofixing at l50C.

The subsequent fixation of the cation-active microbicide concerned maybe effected by causing it to be absorbed by the alkaline-reacting,partially anion-active textile material from an aqueous solution forabout half an hour at 50-60 C.; squeezing off may then be effected andthe textile material freed from unfixed portions of active compound bywashing. The amounts of cation-active microbicides required for thelasting antimicrobial finishing of partially anion-active textilematerial are governed by what is demanded of the finish, and can in eachcase be readily ascertained by preliminary experiments; in general,0.251% in the treatment bath is sufiicient.

The cation-active microbicides concerned are absorbed better and morelastingly on partially anion-active textile material than on normaltextile material; the antimicrobial finish of textile materialattainable with the aid of the process according to the invention istherefore distinguished by a particularly high fastness to washing.v

It is quite surprising that the textile materials produced in accordancewith the invention are microbicidal since it might have been expectedthat the agents would lose their potency when tied to the textilematerial in salt formation. To the contrary, with the aid of the processaccording to the invention, certain hygiene problems, such as may occurin textile materials, can be successfully solved. The process is usefulin the control of pathogenic bacteria and fungi, as well as in avoidingor reducing cross-infections during laundering or other cleaning. Theprocess according to the invention permits the production of autosteriledressings and other microbicidal textile material which can be used inhospitals, for example for wrapping sterilized surgical instruments, orin bacterio EXAMPLE 1 De-sized cotton fabric is treated at 40 C. with asuspension of 2% p-N-( 4,6-dichloro) s triazinylaminobenzoic acid (I) inwater which also contains 0.05%

of a non-ionic wetting'agent; liquor ratio 1:20. After 20 minutes aclear solution is formed, in which 1% sodium carbonate and 30% sodiumchloride are dissolved; after a further 25 minutes at 40 C., the fabricis taken out, squeezed off and transferred for 30 minutes at 40 C. to abath which contains 0.75% 3,4-dichlorobenzyldimethyldodecylammoniumchloride (II); liquor ratio 1:16. Thefabric is then squeezed off,rinsed, soaped (10 minutes boiling in a 0.1% strength solution of ananion-active detergent, liquor ratio 1:20) and watered (24 hours, 20 C.,changes of water per hour, liquor ratio 1: 100). Despite these stresses,the fabric is eminently rot-proof; after 14 days storage in compostsoil, the losses of resistance to tearing are less than 3% As againstthis, fabrics which are treated with (I) or (II) alone in the mannerstated above rot completely (loss of resistance to tearing =100%) afterthese stresses.

EXAMPLE 2 De-sized cotton fabric is treated as stated in Example 1, butinstead of (I), p-N-(4,6-dichloro)-s-triazinylaminobenzenesulfonic acidis used, and instead of 0.75% (II),

0.5% (II) is used. After rinsing, the fabric is soapecl at EXAMPLE 3De-sized cotton fabric is impregnated (2 passages) at room temperaturewith a freshly prepared solution which, per liter contains 50 g. NaOH,25 g. chloroacetic acid and 1 g. of a non-ionic wetting agent. Thefabric is subsequently dried at 120-140 C. for thermofix-ation and thentransferred to a bath having a temperature of 55 C. and containing, perliter, 2.5 g. N -pentachlorophenylhexamethylenediamine acetate; liquorratio 1: 15. The pH of the bath is adjusted to 8.5 after introduction ofthe fabric. After 30 minutes, the fabric is squeezed off, rinsed and, inthe manner indicated in Example 1, watered twice for 24 hours. Evenafter this stress, the fabric is still outstandingly rot-proof; after 14days storage in compost soil, the losses of resistance to tearing are,on average, only about 8% compared with 53% in the case of a notpartially carboxymethylated fabric which was treated in the same mannerwith N -pentachlorophenylhexamethylenediamine acetate.

EXAMPLE 4 De-sized cotton fabric is treated as stated in Example 3, withthe difference that N -pentachlorophenyl-N -dimethylbenzyltrimethylenediaminium chloride is used g./liter) as cation-active compolmd and thereis no regulation of pH. After rinsing, the fabric is, in the mannerindicated in Example 1, watered and tested for resistance to rotting;the losses of resistance to tearing are, on average, 2% compared with100% and 88% respectively, in the case of a fabric which was onlypartially carboxymethylated and a fabric which was only treated with thecation-active compound. If the fabric is tested, as stated in Example 2,for anti-bacterial effectiveness, it is shown that, even after soaping 5times with a non-ionic detergent, the anti-bacterial efliectiveness isretained intact. As against this, a fabric which is notcarboxymethylated, but impregnated with the cation-active compound,exhibits no anti-bacterial effectiveness after rinsing and washing.

EXAMPLE 5 De-sized cotton fabric is treated and tested for resistance torotting in the manner indicated in Example 3 except that, ascation-active compound, N -pentachlorophenyL-N- -dimethyl (3,4-dichloro)benzyltrimethylenediaminium chloride is used (5 g./liter). The losses ofresistance to tearing are on average, 4%, compared with 82% in the caseof a fabric which was only treated with the cation-active compound.

'4. EXAMPLE 6 De-sized cottom fabric is treated as stated in Example 5,with difference that not 5 g./liter but 10 g./liter of cation-activecompound are used. After rinsing and watering, the fabric is 12 timessoaped at the boil or washed 12 times with a commercial cold-washingagent and then, in the manner indicated in Example 2, tested foranti-bacterial effectiveness. In both cases, the fabric still possessesa good anti-bacterial effectiveness. A fabric which was notcarboxymethylated and was only treated with the cation-active compound,however, no longer shows any anti-bacterial effectiveness after soaping5 times or cold-washing 5 times.

EXAMPLE 7 De-sized cotton fabric is impregnated (3 passages) at roomtemperature with a freshly prepared solution which contains per liter,70 g. NaOH and 50 g. chloromethylphosphonic acid. After squeezing off,drying at ISO-140 C. is effected, followed by thermofixation for afurther 5 minutes at 130-140" C., before the fabric is transferred for30 minutes to a bath which, per liter, contains 10 g.benzyldimethyltetradecylammonium chloride. After rinsing and Wateringtwice in the manner indicated in Example 1, testing for resistance torotting is effected: the tear value losses are, on average, 3%. Asagainst this, a fabric treated only with chloromethylphosphonic acid oronly with the cation-active compound rots completely loss of resistanceto tearing).

EXAMPLE 8 De-sized cotton fabric is impregnated (3 passages) with asolution which, per liter, contains 200 g. NaOH, 50 g.acetylenedicarboxylic acid and 1 g. of a non-ionic wetting agent. Aftersqueezing otf, drying at 100 C. is effected, followed by thermofixationfor 10 minutes at 100 C. Treatment with cation-active compound is thencarried out in the manner indicated in Example 2.

Before testing for rot resistance as indicated in Example l, the fabricis watered twice for 24 hours. The fabric proves to be so rot-resistantthat no measurable loss of rot resistance occurs. Moreover, the fabricis outstandingly anti-bacterially effective, even after soaping 12 timeswith a non-ionic detergent; 4 times soaping at the boil with ananion-active detergent likewise does not adversely affect theanti-bacterial effectiveness.

As can be seen from the foregoing examples, the textile material can berendered anion-active by a treatment in fabric form. Alternatively, thetreatment can be carried out on the textile in the form of a yarn orstaple fibers. In the case of synthetic fibers, it is even posible tocarry out the treatment at the resin stage or possible even during theformation of the resin as by copolymerization.

The treatment with the cationic microbicide can similarly be carried outat various stages of processing such as on finished garments, fabrics,yarns, fibers, resins or even monomers. The cationic microbicidetreatment can immediately follow the treatment to render the materialanion-active or it can be carried out one or more steps later.

The number of anion-active sites can be varied widely and the particularselection will depend upon the type and extent of microbicidal treatmentdesired. In addition, if it is intended to use the anion-active textilematerial in the form of a blend, its content of anion-active sites willhave to be greater to impart the desired level of activity to theresulting product. The degree of substitution, however, should not be sogreat that the usual desirable properties of the textile material sufferunduly. The eflicacy and purpose of the microbicidal agent attached tothe anionactive site is also significant. Thus stronger agents can beutilized in lesser amounts; if it is merely desired to prevent growth ofundesirable organisms a lesser amount is needed than if it is desiredthat the textile material actively attack undesired microorganisms inthe vicinity. In addition, the microbicidal agent need not be employedin such quantity as will form salts with all of the anion-active sites,i.e. the desired level of microbicidal activity may be achieved withonly some of the anion-active sites neutralized with microbicide.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that Variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. The process for imparting antimicrobial properties to a textilematerial containing anion-active sites formed by treatment of a textilematerial selected from the group consisting of cotton, rayon, paper,cellulose acetate, polyvinyl alcohol and wool with an acid having anactive site selected from the group consisting of chlormethylphosphonicacid a haloacrylic acid and acetylene monoor dicarboxylic acid, whichcomprises reacting said textile material with a microbicidal quaternaryammonium salt or an N-chlorophenyl-alkylene polyamine, whereby saidrnicrobicide forms a salt with the textile material at said anionactivesites.

' 2. A process according to claim 1 in which the textile material ischemically linked with the reactive compound by treating it with anabout 2-S% strength alkaline aqueous solution of the reactive compoundfor about -40 minutes at about 40-60 C.

3. A process according to claim 2 in which the alkaline aqueous solutioncontains an electrolyte.

4. A process according to claim 3 in which the electrolyte is sodiumchloride or sodium sulfate.

5. A process according to claim 1 in which the textile material ischemically linked with the reactive compound by being impregnated atroom temperature with an alkaline aqueous solution of the reactive ionicsubstance followed by squeezing oflf and thermofixing at about 100- 150C.

6. A process according to claim 6 in which the material undergoes apreliminary drying at about 70 C. after squeezing OE and beforethermofixing.

7. A process according to claim 1 in which the microbicide is fixed tothe anion-active textile material by being absorbed thereon from anaqueous solution in which the textile material is maintained at about50-60" C., followed by squeezing 011 and washing ofi unfixed portions ofactive material.

8. A process according to claim 7 in which the aqueous solution containsabout 0.25 to 1% of the cation-active microbicide.

9. A process according to claim 1 in which the textile material iscellulosic.

10. A process according to claim 9 in which the textile material is acotton-containing fabric.

11. A process according to claim 1 in which said textile materialcomprises a cellulosic material and is rendered anionic-active by beingimpregnated at room temperature with an about 1-5% strength alkalinesolution of acid, the solution containing sodium chloride or sulfate,the textile material being treated for about 10-40 minutes at about40-60 C., then being squeezed oif, thermofixed at about IOU- C., and thecation-active microbicide fixed to the anion-active textile material bybeing absorbed thereon from an about 0.25 to 1% solution in which thetextile material is maintained for about half an hour at about 50-60 C.,followed by squeezing oil and washing olf unfixed portions of activematerial.

12. The textile material produced by the process of claim 1.

13. Textile material according to claim 12 wherein said textile materialis cellulosic.

14. The process according to claim 1 wherein the acid having an activesite is chlormethyl-phosphonic acid.

15. The process according to claim 1 wherein the compound having anactive site is a haloacrylic acid, acetylene monoor di-carboxylic acid.

16. The process of imparting antimicrobial properties to a textilematerial containing anion-active sites formed by treatment of a textilematerial selected from the group consisting of cotton, rayon, paper,cellulose acetate, polyvinyl alcohol and wool, with monochloraceticacid, which comprises reacting said textile material with anN-chlorophenyl-alkylene polyamine to form a salt thereof with thetextile material at said anion-active sites.

References Cited UNITED STATES PATENTS 3,542,504 11/1970 Schofield etal. 117-1385 2,681,846 6/1954 Guthrie et al. 8120 2,729,535 l/ 1956Balassa et al 8116 2,979,374 4/1961 Drake et al 81 16 3,294,779 12/ 1966Bullock et al 8116 3,074,814 1/1963 Sause et al. 117l38.5 2,617,707 11/1952 Daul et al 8120 UX 3,227,614 1/ 1966 Scheuer 424-25 OTHERREFERENCES The Merck Index of Chemicals and Drugs, seventh edition,1960, p. 676.

Gagliardi, American Dyestutf Ref., Ian. 22, 1962, pp. 31-40.

DONALD LEVY, Primary Examiner US. Cl. X.R.

